Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 5(12), 33-37, December (2015) Res. J. Chem. Sci. International Science Congress Association 33 X-Ray Diffraction Study and Biological Analysis of Transition Metal Complexes of N-4-Disubstituted ThiosemicarbazoneGavhane V.S., Rajbhoj A.S. and Gaikwad S.T* Department of Chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad, MS, 431 004, INDIAAvailable online at: www.isca.in, www.isca.me Received 7th November 2015, revised 17th November 2015, accepted 19th December 2015 AbstractComparative studies on the X-ray diffraction parameters of some transition metal complexes like Fe (III), Cu (II), Zn (II) of ligand (L1) has been prepared by using N-4-Ethyl, phenyl-3-thiosemicarbazide and 2-hydroxybenzaldehyde in equimolar ratio. These complexes show various physicochemical properties. X-ray powder diffraction of Fe (III) complex has triclinic crystal system while Cu (II) and Zn (II) complex of ligand (L1) having monoclinic crystal systems with various unit cell parameters. These complexes also tested for biological analysis and shows considerable activity against bacteria and fungi in comparison with standard drug ciprofloxacin. Keywords: N-4-Disubstituted thiosemicarbazone, biological analysis. Introduction Thiosemicarbazones are known as versatile ligands. Thiosemicarbazones and their transition metal complexes having importance in inorganic chemistry and medicinal chemistry1-4. The wavelengths are necessary part of crystal system of metal complexes to determine the peak position, miller indices (h, k, l) values, unit cell parameters and 2 value with radiation source of CuK by used as X-ray diffractometer range5-6. The target of X-ray diffraction is to determine the probable structure of the metal complexes. To accomplish this target we must be able to express mathematically the nature of the measured interference pattern in terms of the position of the various atoms within the crystal. To determine the crystalline compounds they are using XRD instrumental technique. Literature survey shows that transition metal complexes generally crystalline as well as amorphous in nature with tetrahedral, octahedral or square planar geometry. In present paper the powder X-ray diffraction of Fe (III), Cu (II) and Zn (II) complexes of N-4-disubstituted thiosemicarbazones scanned in the range of 0-80 at wavelength 1.540598Å. Biological analysis of complexes was tested on Staphylococcus aureus, Bacillus substilis, Aspergillus niger and Fusarium oxysporium species. Material and Methods All chemicals and solvents used were of A. R. grade and used as received. The transition metal salts (Metal chlorides) obtained from Aldrich. The powder XRD was recorded on Perkin Elmer TA/SDT-2960 and Philips 3701, respectively at the range of 0-80 at wavelength 1.540598Å. Synthesis of Schiff base ligand: The Schiff base (E)-1-(2-hydroxybenzylidene)-4-ethyl-4-phenyl thiosemicarbazide (L1) prepared by modifying reported method of scovil10. 2-hydroxybenzaldehyde (0.1mol) and N-4-ethyl, phenyl-3-thiosemicarbazide refluxed for 30 minutes. The yellow solid formed was filtered, washed with ether, dried in the desiccators and recrystallized with hot ethanol-DCM (1:2) proportion. Yield: 80%. Synthesis of Metal complexes: Hot methanolic solution (0.1mmol) of metal salt is mixed with (0.2mmol) solution of (E)-1- (2-hydroxybenzylidene) -4-ethyl-4-phenyl thiosemicarbazide (L1). The resulting solution mixture was refluxed for 2-3 hours and allowed to kept overnight at room temperature. The precipitated complex were filtered off, washed with ether, water and dried in vacuum over anhydrous calcium chloride in desiccators. The complexes obtained are microcrystalline solids which are stable in air and decompose above 300C. They are insoluble in organic solvents such as acetone, chloroform but soluble in DMF and DMSO. Results and Discussion The X-ray diffractogram of some transition metal complexes of ligand (L1) are crystalline as well as amorphous in nature. To determine the h,k,l values of reflection by using reported methods11. The X-ray diffraction was performed to obtain further evidence about the structure of the metal complexes. The diffractogram obtained for the Fe (III), Cu (II) and Zn (II) complexes were given in figures-1, 2, 3. And the XRD patterns indicated crystalline nature of Zn (II) complex while Fe (III) and Cu (II) complexes are amorphous in nature. The values of sin 2 d for each peak have been determined by cell parameters and corresponding h, k, l values. The lattice constants a, b and c for each unit cell have been found out and given tables-1 to 4. The XRD patterns the major peak which showed relative intensity greater than 10% indexed by computer programme12. Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 33-37, December (2015) Res. J. Chem. Sci. International Science Congress Association 34 Experimental density values of the complexes were determined by using specific gravity method13. In a figure 1-3 show that the relative intensity vs. 2 values. Biological Analysis: Antimicrobial and Antifungal activity: Derivatives of thiosemicarbazones and their transition metal complexes exhibit a wide variety of biological activity14. The antimicrobial and antifungal activity of ligand and their transition metal complexes were carried out successfully on Aspergillus niger, Fusarium oxasporium, Staphylococcus aureus and Bacillus substilis species. The results show that the ligand as well as metal complexes are more active against bacteria and fungi and shows almost equal activity of standard ciprofloxacin shown in table-5. 010203040506070805000100001500020000250003000035000 Intensity2 Theta(degrees)Figure-1 Xray diffractogram of [Fe (L1)] Complex0102030405060708020004000600080001000012000140001600018000 Intensity2Theta(degees)Figure-2 Xray diffractogram of [Cu (L1)] Complex Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 33-37, December (2015) Res. J. Chem. Sci. International Science Congress Association 35 0102030405060708050001000015000200002500030000 Intensity2Theta(degrees)Figure-3 Xray diffractogram of [Zn (L1)(HO)] ComplexTable-1 Lattice constant, unit cell volume, Crystal system, Inter-planar spacing of metalUnit cell of complexes Lattice constant Unit cell Volume Inter axial angle Crystal system d value Å a (Å) b (Å) c (Å) Fe(III) 15.23 10.32 7.89 111.6 =90 Monoclinic 12.25 7.21 Cu(II) 14.26 10.02 14.23 203.5 =90 Monoclinic 12.55 7.04 Zn(II) 9.32 10.23 8.23 785.6 90 Triclinic 8.38 10.53 Table-2 Millar indices and interplanar distances of Fe (III) complex(Cal) 2(Obs) h K L d (Obs) d (Cal) Intensity (%) 12.25 12.46 0 0 1 7.21 7.09 100 20.88 20.56 -1 2 1 4.25 4.31 68.75 17.47 17.16 0 2 0 5.06 5.16 55.86 25.21 25.07 0 0 2 3.52 3.54 40.30 13.96 14.14 -1 1 1 6.33 6.25 16.72 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 33-37, December (2015) Res. J. Chem. Sci. International Science Congress Association 36 Table-3 Millar indices and interplanar distances of Cu (II) complex(Cal) 2(Obs) h K L d (Obs) d (Cal) Intensity (%) 6.22 6.27 -1 0 0 14.19 14.06 42.20 9.95 9.60 1 0 1 8.88 9.19 50.04 9.60 9.60 1 0 1 9.26 9.19 58.18 8.45 8.11 -1 0 1 10.48 10.88 4.10 15.37 15.37 -2 1 0 5.75 5.75 10.90 Table-4 Millar indices and interplanar distances of Zn (II) complex(Cal) 2(Obs) H K L d (Obs) d (Cal) Intensity (%) 19.62 19.49 1 -2 0 4.51 4.55 18.67 8.38 8.63 0 -1 0 10.53 10.22 100 17.75 17.32 0 -2 0 4.99 5.11 8.39 11.23 10.73 0 0 1 8.28 8.23 4.05 21.37 21.20 -2 -1 0 4.15 4.18 6.04 Table-5 Antimicrobial and Antifungal activity of ligand (L1) and its transition metal complexes Ligand/metal complex Antibacterial activity Antifungal activity Staphylococcus aureus Bacillus substilis Aspergillus niger Fusarium oxysporium 250ppm 500ppm 250ppm 500ppm 250ppm 500ppm 250ppm 500ppm Ligand (L1) 16 20 20 23 19 22 20 22 Fe(III) 17 20 22 25 19 20 19 22 Cu (II) 22 27 26 30 18 19 25 28 Zn (II) 17 17 20 24 22 24 23 23 Ciprofloxacin 34 36 43 45 22 24 31 38 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 5(12), 33-37, December (2015) Res. J. Chem. Sci. International Science Congress Association 37 Figure-4 Comparative study of antimicrobial and antifungal activity of ligand (L1) and its metal complexesConclusion The transition metal complexes like Fe (III), Cu (II), and Zn (II) of O, N and S donor thiosemicarbazone ligand (L1) were studied by X-ray diffraction. The X-ray diffraction studies of Fe (III) complex having monoclinic crystal system with Z = 1 while Cu (II) complex also monoclinic with Z = 1 and are amorphous in nature. Zn (II) complex having triclinic crystal system with Z = 1 are crystalline in nature and having octahedral geometry. These metal complexes of thiosemicarbazones are biologically active. Acknowledgement The authors are grateful to the Head, department of chemistry, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad for providing laboratory facility and financial assistance of UGC (SAP), DIST-FIST. References 1.Sadler P. J., Gun Z., Pure Appl. Chem, 70, 863 (1998)2.Sadler P. J., Adv. 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